US3632389A - Process for the surface treatment of copper and its alloys - Google Patents

Process for the surface treatment of copper and its alloys Download PDF

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Publication number
US3632389A
US3632389A US3632389DA US3632389A US 3632389 A US3632389 A US 3632389A US 3632389D A US3632389D A US 3632389DA US 3632389 A US3632389 A US 3632389A
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United States
Prior art keywords
solution
copper
percent
chromate
alloys
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Expired - Lifetime
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English (en)
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Hargovind N Vazirani
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AT&T Corp
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Bell Telephone Laboratories Inc
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/38—Chromatising
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31529—Next to metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31605—Next to free metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer

Definitions

  • FIGURE is a cross-sectional view of a laminate formed according to the inventive process.
  • Preliminary cleaning is generally divided into degreasing and descaling.
  • degreasing is generally effective in removing only oils and grease and is ineffective in removing corrosion products such as naturally formed oxide scale.
  • Descaling which may be either mechanical or chemical, will, however, generally remove substantially all of the surface contamination. However, descaling chemically without first degreasing may result in rapid contamination of the solution.
  • Removal of oils and grease may be accomplished by the use of organic solvents such as alcohols, ketones and chlorinated solvents such as trichlorethylene and perchlorethylene. Such removal may also be accomplished by use of alkaline cleaners.
  • organic solvents such as alcohols, ketones and chlorinated solvents such as trichlorethylene and perchlorethylene.
  • alkaline cleaners Commonly used components of such cleaning mixtures are: sodium hydroxide, used for its saponifying power; phosphates and silicates, used for their emulsifying and wetting abilities; surface active agents such as alkyl aryl polyether alcohols, used for their wetting ability; and detergents, used for their wetting and saponifying ability.
  • an effective alkaline cleaning solution is one which contains from 1 to l0 percent by weight sodium metasilicate, from 1 to 10 percent trisodium phosphate and from I to 10 percent of an alkyl aryl polyether alcohol, remainder water. Cleaning in this solution may be carried out from from 1 to 30 minutes at a temperature of from 70 to Descaling is usually accomplished by the use of acid solutions or by mechanical abrasion. The particular method chosen for descaling will depend on the thickness, composition and character of the scale, which depends upon the composition and character of the scale, which depends upon the composition of the metal and upon its history, particularly its thermal history.
  • aqueous solution containing from 1 to 10 percent by weight of nitric acid, immersing the metal therein at a temperature of from 70 to F. for from I to 30 minutes.
  • phosphoric acid to increase the acidity of the solution.
  • Such a solution contains up to 80 percent by weight phosphoric acid, up to 40 percent by weight nitric acid, remainder at less 20 percent water, and is used within the same temperature range as is the nitric acid solution.
  • Examples of mechanical abrasion methods for descaling are abrasive blasting, wire brushing, and grinding. In general, these methods are more wasteful of metal and produce surfaces somewhat rougher textured than do solution methods. However, rough surfaces are particularly advantageous for increased peel strength of subsequently formed joints. Sandblasting is often used for this reason. In operation, grit or sand which passes a standard screen from No. 150 to 500 is introduced into an air stream at pressures of 25 to about I00 pounds per square inch and the blast directed over the surface of the metal until the scale is removed.
  • a rough surface may also be achieved chemically of course, as for example, by adjusting the concentration of an acid pickling bath to a high concentration of nitric acid within the ranges described or by using a chemical etching solution containing for example hydrochloric acid and either ferric chloride or cupric chloride each in the amounts of from 1 to 10 percent by weight.
  • the clean metal surface should be either treated with chromate solution promptly or stored under noncorrosive conditions until treatment in order to realize any advantage gained, since exposure of the clean surface to a nonprotective atmosphere will soon result in reformation of corrosion products.
  • the concentration of chromate ions in the solution is not critical and may range from 0.00l percent by weight to saturation.
  • the ions may be introduced in combination with the Group 1 alkali metals; lithium, sodium, potassium, rubidium and cesium or the Group ll alkaline earth metals; beryllium, magnesium, calcium, strontium and barium. It is essential that the solution have a pH of at least 4 in order to minimize the formation of chromic acid in the solution, which would tend to dissolve the formed surface. A pH of from 8 to is preferred for this purpose.
  • a preferred embodiment of the treatment of the metal surface comprisfi inserting the metal and some other suitable electrode material into the solution, and applying a voltage so that the metal is treated cathodically.
  • a voltage of from 1 to 20 is required, below which range the voltage is insufiicient to reduce the oxide scale on the metal surface and above which range gassing of hydrogen becomes excessive, thus interfering with the formation of a suitable surface. Within this range, a voltage of from 2 to 6 is preferred for optimum results.
  • the oxide scale will ordinarily be removed within 10 seconds, but can be substantially removed within 1 second. However, it is preferred to continue passage of current for from /2 to 1 minute in order to minimize the possibility of not reducing all the oxide from recessed parts.
  • the formation of the chromate layer is self-limiting so that excessive treatment times will not substantially impair the final result.
  • EXAMPLE 1 Three sets of T-peel joints were made from soft copper 0.032 inch thick, and 1 inch wide and two acrylic acidethylene copolymers are per ASTM procedure DlB'Ifi-GIT. All the specimens were vapor degreased. Sets 2 and 3 were then acid etched in a solution containing phosphoric acid, nitric acid and water in the amounts of 75 percent, 10 percent and percent by weight, respectively, for one-half minute, followed by rinsing with distilled water. Set 2 was then contacted with a chlorite ion-containing solution for 2 minutes at 205 F.
  • Set 3 was treated cathodically at 3 volts for 3 minutes in a room-temperature solution containing 3 percent by weight each of sodium chromate, sodium carbonate and sodium citrate. Each set was then rinsed with distilled water and air dried at room temperature and joined. The sets were then measured for T-peel strength according to ASTM procedure Dl87-6lbT. The results for each copolymer are shown in ta-65 bles 1A and 18, respectively.
  • EXAMPLE 2 Three sets of standard Va-inch lap joints were made from Muntz metal, (60 percent copper 40 percent zinc) and epoxy resin as per ASTM procedure Dl002. The specimens were vapor degreased with trichlorethylene. Sets 2 and 3 were then acid etched as in example 1. Set 2 was treated with a chlorite solution for 2 minutes at 205 F. Set 3 was treated cathodically at 4 1% volts in a solution containing 3 percent each of sodium chromate, sodium carbonate and sodium citrate for 1 minute. Each set was then rinsed with distilled water, air dried and joined. The sets were then measured for tensile shear strength according to ASTM procedure D1 ,002. Permanence was also measured by observing the time to failure when a static load was applied for six specimens in an ambient atmosphere of 95 F. at 90 percent relative humidity. Results are shown in table 2.
  • step of contacting said surface as a cathode with said solution is following by joining said surface to an organic polymer selected from the group consisting of carboxyl-olefin epoxies, nitrile rubber phenolics, polyvinyl butyrals, polyvinyl formals, alkyds, acrylics, polyesters, polyurethanes and silicones.
  • organic polymer selected from the group consisting of carboxyl-olefin epoxies, nitrile rubber phenolics, polyvinyl butyrals, polyvinyl formals, alkyds, acrylics, polyesters, polyurethanes and silicones.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Electrochemical Coating By Surface Reaction (AREA)
  • Pressure Welding/Diffusion-Bonding (AREA)
US3632389D 1968-04-03 1968-04-03 Process for the surface treatment of copper and its alloys Expired - Lifetime US3632389A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US71851768A 1968-04-03 1968-04-03

Publications (1)

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US3632389A true US3632389A (en) 1972-01-04

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US3632389D Expired - Lifetime US3632389A (en) 1968-04-03 1968-04-03 Process for the surface treatment of copper and its alloys

Country Status (7)

Country Link
US (1) US3632389A (de)
JP (1) JPS4934179B1 (de)
BE (1) BE730853A (de)
CA (1) CA923843A (de)
DE (1) DE1912542C3 (de)
FR (1) FR2005445A1 (de)
GB (1) GB1259972A (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4071417A (en) * 1977-06-29 1978-01-31 Bell Telephone Laboratories, Incorporated Process for decreasing the porosity of gold
US4077852A (en) * 1977-02-09 1978-03-07 Bell Telephone Laboratories, Incorporated Selective gold plating
US4077851A (en) * 1977-03-04 1978-03-07 Bell Telephone Laboratories, Incorporated Patterned chromate film process
US4082620A (en) * 1977-04-29 1978-04-04 Bell Telephone Laboratories, Incorporated Process for chromating metallic surfaces
US6179990B1 (en) 1999-06-30 2001-01-30 International Business Machines Corporation Biased acid cleaning of a copper-invar-copper laminate
US20020164426A1 (en) * 1999-09-23 2002-11-07 Ennis Thomas James Method of adhering coatings to substrates
US11230782B2 (en) * 2018-01-04 2022-01-25 Samsung Electronics Co., Ltd. Passivation surface treatment of stainless steel

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2206064A (en) * 1936-09-16 1940-07-02 Patents Corp Metal treating process
US2377229A (en) * 1937-07-03 1945-05-29 Little Inc A Electrolytic deposition of chromium
US2678299A (en) * 1946-10-04 1954-05-11 Printing Dev Inc Method of making planographic printing plates
US3129149A (en) * 1961-05-08 1964-04-14 M & T Chemicals Inc Chromium plating process
US3451871A (en) * 1964-05-26 1969-06-24 Rheinische Blattmetall Ag Method of treating metallic surfaces
US3454474A (en) * 1966-11-23 1969-07-08 Corillium Corp Chromium plating process
US3475295A (en) * 1967-03-28 1969-10-28 Nat Steel Corp Electrodeposition of chromium-containing films on ferrous metal articles

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2206064A (en) * 1936-09-16 1940-07-02 Patents Corp Metal treating process
US2377229A (en) * 1937-07-03 1945-05-29 Little Inc A Electrolytic deposition of chromium
US2678299A (en) * 1946-10-04 1954-05-11 Printing Dev Inc Method of making planographic printing plates
US3129149A (en) * 1961-05-08 1964-04-14 M & T Chemicals Inc Chromium plating process
US3451871A (en) * 1964-05-26 1969-06-24 Rheinische Blattmetall Ag Method of treating metallic surfaces
US3454474A (en) * 1966-11-23 1969-07-08 Corillium Corp Chromium plating process
US3475295A (en) * 1967-03-28 1969-10-28 Nat Steel Corp Electrodeposition of chromium-containing films on ferrous metal articles

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4077852A (en) * 1977-02-09 1978-03-07 Bell Telephone Laboratories, Incorporated Selective gold plating
US4077851A (en) * 1977-03-04 1978-03-07 Bell Telephone Laboratories, Incorporated Patterned chromate film process
US4082620A (en) * 1977-04-29 1978-04-04 Bell Telephone Laboratories, Incorporated Process for chromating metallic surfaces
US4071417A (en) * 1977-06-29 1978-01-31 Bell Telephone Laboratories, Incorporated Process for decreasing the porosity of gold
US6179990B1 (en) 1999-06-30 2001-01-30 International Business Machines Corporation Biased acid cleaning of a copper-invar-copper laminate
US20020164426A1 (en) * 1999-09-23 2002-11-07 Ennis Thomas James Method of adhering coatings to substrates
US11230782B2 (en) * 2018-01-04 2022-01-25 Samsung Electronics Co., Ltd. Passivation surface treatment of stainless steel

Also Published As

Publication number Publication date
DE1912542B2 (de) 1977-09-15
DE1912542A1 (de) 1969-10-30
JPS4934179B1 (de) 1974-09-12
CA923843A (en) 1973-04-03
DE1912542C3 (de) 1978-05-11
BE730853A (de) 1969-09-15
GB1259972A (en) 1972-01-12
FR2005445A1 (de) 1969-12-12

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